Process of and apparatus for breaking up the components of petroleum and the like into more volatile products



July 12, 1927.

W. C. WELLS ET AL PROCESS OF AND APPARATUS FOR BREAKING UP THE COMPONENTS OF PETROLEUM AND THE LIKE INTO MORE 'VOLATILE PRODUCTS Filed Aug. 10, 1920 Patented July 12, 1927.

WILLET C. WELLS AND FRANK E. WELLS, OF GOLUUS, OHIO PROCESS 035 AND APPARATUS FOR BREAKING UP THE COMPONENTS OF PET AND THE LIKE INTO MORE VQLATILE PEODUG'IS.

Application filed August 10, 1920. Serial No. $02,536.

Our invention relates to improvements in the process of, and apparatus for breaking up petroleunis and the distillates and residues-of petroleums and the like which are not suificiently volatile tobe classed as motor spirits or gasoline, and by the practice of our invention we convert a great portion of such materials into the equivalent of natural gasoline with no liquid residue; the remainder'of such materials is commercial illuminating gas and carbon. The current method of breaking up hydrocarbons is to subject them to pressure in a still containing a large quantity of hydrocarbons,

to raise the boiling point to the temperature necessary to decompose the same. Butithere are vital objections to this treatment, namely,-when a considerable body of hydrocarbon is raised to a high temperature under great pressure in a stlll, a very hazardous condition is created; also, thecarbon'produced in the process rapidly coats the still bottom and thus insulates it to such an extent that the degree of heat to which the still bottom is subjected to produce proper results greatly weakens the still bottom, so that the limit of safety is reached by the time half of the charge is driven off; and from this fifty per cent taken off not more than fifty to fifty-five per cent will make marketable gasoline, while the remaining seventy or more per cent of the original charge must be used for other purposes and at a lower market value than when it was placed in the still. Consequently, there must under present conditions be an ex ressive margin between the cost of gasoline and the cost of thematerials used to produce gasoline. Still further, the bituminous matter in residue fuel oils and like heavy hydrocarbons coats the still bottom so quickly with carbon in this current method of treatment as to prohibit their use in the production of gasoline therefrom.

Many attempts have been made to improve the method above described for the utilization of all the marketable portions of hylrocarbons; among these is the method of carbon in heated lead contained in pendant tubes or pockets opening out of the still bottom, of such length that the weight of the lead at the bottom of the column of which the hydrocarbon is introduced is regarded as an important pressure feature. I

These and other methods have been and are being tried but we have found serious objections to them all which render their use for commercial purposes practically prohibitive. form and soon clog an unprotected tube or pipe which conveys the hydrocarbon to submergence in the leadbath having "a sumcient temperature to break up the hydrocarbons being treated; also that .hydrocar- 7 bons decomposed in such bath will deposit carbon mixed with sufiicientj bituminous matter to envelope and retain the spray of the violently bubbling lead, and thereby rapidly form cakes of coke ermeated with lead, and these rigidly attac themselvesto the sides of the still and the tubes through which the hydrocarbon is introduced. This lead filled coke, when cold, resembles a sponge filled with set cement. We have also found that the difference in the extent of the expansion of the lead and the metal pocket or tube containing the lead, at the degree of heat required in the process, is so great that the tube is certain torupture as readily as if water were frozen therein. Further, if the hydrocarbon is left in the tube or pipe through which it is introduced into the bottom of the liquid bath, at the close of operation, the heat of the bath will break up the en hydrocarbon thus remaining in the tube and will soon close the said tube with carbon at the top of the bath. These discoveries of ours have shown that motor spirits can not be successfully produced with the methods as described as in current use; therefore the conception that the mere submergence of hydrocarbons in a sufficiently heated permanent fluid bath of suflicient gravity to float the carbon formed, is an open door to loo successful commercial operation, is quite delusive.

Our improvements create a process which avoids all the objections above outlined and 1s thoroughly adapted to commercial use, [0e

and the apparatus shown in the drawings presents a satisfactory embodiment of our invention. Referring to the drawings which are hereto attached and are hereby made a part of this specification,

We have found that carbon 'will Fig. 1, is a vertical Ill sectional view of the cracking apparatus, showing the burners, connections for admitting compressed gas into the tubes or pipes through which the hydrocarbon passes to submer ence for the'pu'rpose of displacing .the-hy rocarbon remaining therein at the closeof operation, the condenser, the supply tank, the tank which receives the mixed carbon and hydrocarbon from the retort or still, and the press wherein the carbon is separatedjfrom, the hydrocarbon. Fig. 2 is an enlarged sectional view of one of the pendant tubes or pockets, designated at 3. Fig. 3 is an enlarged sectional view of a thermostat; Fig. 4 is a cross section along the line AA of Fig. 2, showing the detailed construction of the hydrocarbon inlet tube or pipe and its casings or coverings designated for its protection against the heat, as above mentioned. a

The description of the apparatus will now be given in describing the operation thereof in the performance of our process. 1 is the still and 2 is the furnace having two burners thereimshown at 38 and 39; 38 is the upper one which is used at the beginning of operations to;heat the lead 4 contained in the pendant closed tubes or pockets 3 at the upper open end thereof, whereby the lead is permitted to expand into the bottom of the still and rupture of the pendant tube is avoided. The heat from burner 38 is applied to the bottom of the still also, and the lead bath therein is heated at the same time as the lead in the pendant tubes. The heating of the lead in the pendant tubes proceeds from the top downwardly, and when this is sufficiently accomplished the burner 39 is started and 38 is shut off, and the heat thereafter needed in the operation is supplied from burner 39. 1

In filling the pendant tubes 3 with lead they are poured full and the lead is permitted to run over the top and spread over the bottom of the still, and hence the lead bath in the still and in the pendant tubes or pockets is a continuous body, and is brought to a uniform degree of heat as described. The lead bath on the still bottom is shown at 5.

6 is the still covering or cap through which is fitted the tube 7 having its lower end closed, and thereinto is inserted the pyronieter point 10, having the usual electric connections: the point 10 is inserted to reach to the bottom of the tube 7 which extends int-o the lower portion of the pocket or pendant tube 3. 8 is the casing containing the hydrocarbon inlet tube 12, and the construction thereof is most clearly shown in Fig, 4; tube 12 is encased by tube 8 which in turn is provided with an asbestos jacket 8', which is encased within the outer tube 8, and by means of these coverings the inner tube 12 through which the hydrocarbon is delivered sion increases unil it is sufiicient to into the bottom of the lead bath in the pendant tube 3, is protected against the heat in the body of the still and the hydrocarbon can thus be introduced into the bottom of the lead bath before decomposition takes place.

"until it reaches the bottom thereof. In Fig.

2 it clearly appears that the pyro-meter point, the thermostat tube and the inlet tube for the hydrocarbon, all extend nearly to the bottom of the lead bath in the pendant tube or pocket 3, and hence all are subject to the degree ofheat there prevailing, where the hydrocarbon first becomes subject to the decomposing influence of the heat; it is also noticed that these encasing tubes described are positioned alike in the lead bath 5 in the still, and throughout their lengths are subject to exactly the same heat conditions.

The hydrocarbon treated in the operation is shown in a tank at 13 from which it is pumped, at the beginning of the operation, through pipe 15, the valve 15 being closed, through valve 31 into pipe 31, into pipe 25 until it overlies the lead bath 5 in the bot tom of the still and overflows through pipe 27, leaving a body of hydrocarbon indicated at 26 in the still at the time-the operation is begun: Thereupon valve 31 is nearly or quite closed, valve 15 is opened, and the pumping continues and the hydrocarbon flows on through pipe 15 into pi e 16 and so into the chamber 17' of the t ermostat box 17. Within box 17 is the diaphragm 35 carrying the valve stem 36 with the tapered valve 36* at the end thereof, projecting through the opening in the wall 17"; the valve 36 is engaged by the spring 36 whose tension is fixed by the screw 17 adjustable from the outside of the box 17. The be havior of the apparatus here described is as follows :The air in the thermostat tube 11 is expanded by the heat prevailing in the lead bath at the bottom and throughout the extent of the pocket or tube 3, and the expanress inwardly the diaphragm 35 against tie pressure exerted thereagainst by thehydrocarbon introduced into the box through pipe 16 as described, and also against thetension of the spring 36 upon the valve 36. Thereupon the hydrocarbon flows into tube 12 through valve opening at 36*, and passes on down through the tube 12 into the lead bath at the bottom of the pendant tube or pocket 3 as clearly appears in Fig. 2. When the'incoming hydrocarbon has entered in quantity sufficient to influence the degree of heat prevailing therein so as to lessen the expansion of the air in the thermostat tube, diaphra m 35 will retreat towards its normal position and partially cut off the inflow of hydrocarmatically establishing conditions of thermal equilibrium in the lead bath.

The weighted valve 39 on from tank 13 to pipe 15'assures uniform pressure in the chamber 17 of thermostat box 17 regardless of the volume of the hydrocarbonintroduced thereinto. When the first hydrocarbon is admitted through the thermostat box as above described, it enters the tube 12 with pressure of 10 pounds or enough to expel from the lower end of said tube 12 of 19 inches length the lead therein and drive it out into the surrounding body of the lead, and thereupon the hydrocarbon issues in a fine stream into the lead bath at the bottom of tube 3; the vapor from the; hydrocarbon ascends through the lead bath and violently agitates the lead into uniform temperature throughout. Thus, on account of the columnar form of the lead bath in the pendant tubes the vapors are kept long enough within the body'of the lead ath in their passage therethrough to subject them all alike to a uniform decomposing temperature; varying with different hydrocarbons from 850 to 1175 Fahr. -As these vapors rise through the overlying hydrocarbon they deposit the carbon produced in the operation therein, where it becomes thoroughly mixed therewith by the violently bubbling lead. The vapors pass from the. retort through pipes 18 and 19 and through vapor line 19? to the aerial condenser; the condensate in the first section 20 is returned throughpipe 24 and-pipe 25 to the still. The vapors condensedin the succeeding sections 21 and 22 are trapped ofi at 32 and 33 to their respective containers, the portions which are sufficiently volatile for use are evaporated therefrom and the remainder is returned to tank 13 in a manner not necessary to be shown herein, for a repetition of the operation. The fixed gas and vapors passing section 22 pass on' through water cooled sec tion of condenser 23 and the condensate is trapped off at 34, being motor spirits; the fixed gas is conveyed awayv through the pipe 37 and may be subjected to compressing or absorptive process to obtain light oils therefrom. v

If the condensate from section 20 should be insuflicient to supply the volume of hydrocarbon necessary to carry out the carbon produced in the still, valve connection 31 can be opened to admit hydrocarbon from tank 13 to maintain an overflow through pipe 27 into tank 28; thence the mixture of carbon and hydrocarbon drawn off continuously fromthe surface of the lead bath in the still is pumped into press 29; here the carbon isiretained in cakes, and the hydrocarbon is'returned through pipe 30 to whence it is pumped into the still.

tank 13 the bypass 4 0- form temperature submergence in the lead bath, as described. When the flow of hydrocarbon into the lower portion of pendant tubes 3 ceases for any reason, valve 15 is closed, and valve 15 is opened; a supply of compressed gas is then admitted through pipe 15 into pipe 15- and into the. tubes 16, through the thermostat .box into pipes for treatment by 12, and thereby the'hydrocarbon remaimng therein is expelled .out into the lead bath, and the deposit of carbon therein, mentioned hereinabove, is prevented.

To summarize our improvements we may set forth the features as follows, to emphasize the contrast with current methods By means of tubes or pockets pendant from the still We obtain the maximum heating surface, and by the use of molten lead or its equivalent "in said tubes and covering the floor of the still carbon is prevented from adhering to the heating surface; by melting the lead in the tubes upon beginning the, operation, from the top downwards, rupture of the tubes from the unequal expansion of the evaporating therein, and consequently the formation of carbon in said tubes is prevented; such formation would closethe tubes and of course interfere with successful operation. By introducing the hydrocarbon to be broken up into the lead atthe bottom of said tubes, heat is taken up and thelead is violently agitated by the vapors from the hydrocarbon, and thus the lead, by convexion, becomes a medium to transfer unito the hydrocarbon injected thereinto and the vapors therefrom in their rise through the depths of the heated lead in the pendant tubes; and by means of thermostat control of the volume\ of hydrocarbon entering each tube, equilibrium of temperature is maintained therein between the heat absorbed in breaking up the hydro-' carbons and the heat applied to the hydrocarbon; the vapors in their passage through the body of the hydrocarbon overlying the lead bath on the floor of the still, deposit the carbon they carry therein, and it is thoroughly mixed with the hydrocarbon. by the violent ebullition' of the lead, and this mixture is caused to flow continuously from the still by the continuous introduction of a supply of hydrocarbon into the still above (Ill returned for further breaking up as def scribed; the final products arecommercial vaporization and decomposition beneath a molten metal bath contained in a. retort,

Withdrawing the resulting vapors and gases from the upper part of the ,retort, conveying them away and condensing them, maintaining a continuously moving body of hydrocarbon oil on the surface of said molten metal bath, continuously removing said body of hydrocarbon oil from the retort, separating therefrom carbon resulting from the decomposition, and returning the body of oil to the retort for s'ubmergence beneath the molten metal bath.

2. The process of breaking uphydrocarbons into more volatile products by submerging them for decomposition in a heated molten metal bath which consists in protecting incoming streams of hydrocarbon against decomposing temperature in the ducts through which they are introduced into said bath, subjecting the said hydrocarbon to the heat of said bath, subjecting all of the vapors thus produced to uniform degree of heat in their passage through said bath to the surface thereof, and expelling all hydrocarbon from said ducts when operation ceases by the introduction into said ducts of compressed gas.

3. The process of converting hydrocarbon into more volatile products, which consists in 'submerging said hydrocarbon for decomposition intoa column of heated molten metal bath b introducing said hydrocar-= bon into the fbwer portion of said column; protecting the hydrocarbon from decomposition by heat in their course to submergence; controlling the temperature of the said column of molten metal by automatically controlling the volume of hydrocarbon being introduced thereinto; maintaining a continuously moving body of oilonthe surface of said metal whereby the carbon resulting from the decomposition is continuously removed from the system.

4;. The process of breaking up hydrocarif bons into more volatile products which con to rise and pass sists in submerging said hydrocarbon by introduction thereof in streams through heat protected tubes into heated columns of a molten metal bath contained in tubes suspended from the bottom of a retort, vaporizing, and decomposing said hydrocarbon in said bath. allowing the vaporsthus produced through a body of hydrocarbon overlying said bath and kept at a lower temperature than the decomposing temperature of the bath in said columns by the return thereinto of the condensate of the the carbon from the said supply,

. teatime less volatile portion of the vapors produced in the process, mixing the carbonformed by the operation with said body of hydrocarbon by the passage of vapors therethrough,

and continuously tra ping ofl the mixture of carbon and hydrocar on thus produced.

5. In the cracking of hydrocarbon oils the described process consistingin passing the oil to be treated before it has become'evap- .orated or dissociated through a molten metal bath in a retort, collecting the resulting ing vapors and gases in the upper part of the retort, conveying them away from the retort through an upwardly extendingduct, condensing the vapors, continuously supplying to and withdrawing from the surface of the bath a layer of the heavy fractions and unvaporized hydrocarbons, among them the condensate and backflow from said duct, which layer holds the carbon impurities in suspension. andregulat-ing the supply of the material to form the layer as required.

7. The process of'converting hydrocarbon oil into more volatile products, which con sists in submerging said hydrocarbon oil for evaporation and decomposition beneath a molten metal bath contained in a retort, protecting the hydrocarbon oil from the effects of heat sufficient to decompose until delivered beneath the bath, withdrawing the resulting vapors and gases from the upper part of the retort, conveying them away and condensing them, constantly sup lying hydrocarbon oil on the surface 0 saidmolten metal bath to float the carbon formed, continuously withdrawing hydrocarbon oil and separating therefrom carbon resulting from the decomposition, and returning all of the oil freed from carbon to the retort for submergence beneath the molten metal bath,

8. The process of breaking up the heavy products of petroleum, and the like, into more volatile products, which consists in introducing the petroleum into the lower portion of a, plurality of chambers depending from and orming part of the bottom' of a still, maintaining a protect-ing medium for the petroleum whereby it is unaffected by the heat prior to its admission directly into the lower portions of said chambers, maintaining in said chambers and on 'the said bottom of the still a bath of nonevaporable molten metal, and maintaining on the surface of said metal on the bottom of the still a layer of hydrocarbon oil which sustains the carbon formed, permitting the material under'treatment to pass through the molten bath and through said layer of hydrocarbon oil, permitting the resultant vapors to escape andcondense, and removing hydrocarbon oil from the surface of the bath.

9. In the cracking of hydrocarbon oils, the described process consisting in passing the oil to be treated through a molten metal bath in a retort, collecting the resulting 'vapors .and gases in the upperwpart of the retort,

conveying them away and condensing them, and continuously supplying to and continuously withdrawing from the surface of the bath a la er of the heavy fractions and unvaporize hydrocarbons which holds the carbon impurities in suspension, and continuousl separating the carbon therefrom.

10. The process of breaking up the heavy products of petroleum, and the like, into more' volatile products, which consists in introducing the petroleum into the lower portions of a lurality of chambers depending from and orming part of the bottom of a still, maintaining a protecting medium for the petroleum whereby to prevent decomposition prior to its admission directly into the lower portions of said chambers, maintaining in said chambers and on the said bottom of the still a bath of nonevaporable molten metal, and maintaining on the surface of said metal on the bottom of the still a layer of hydrocarbon oil, which sustains the carbon formed, permitting the material under treatment to pass throu h the molten bath and through said layer 0 hydrocarbon oil, permitting the resultant va ore to escape and condense, removing hy rocarbon oil from the surface of the bath,'separating the carbon from the latter, and returning to the still the oil fromwhich the carbon has been removed.

11. In an apparatu for converting hydrocarbon oils into more volatile products, the combination of a retort containing a molten metal bath, said retort having adjacent its top an opening for vapors, a condenser for receiving said vapors, conduits-leading into the retort and havin an outlet adjacent the bottom of the retort for submerging said hydrocarbon oils beneath the molten bath, means for maintaining a body of hydrocarbon oil on the surface of the molten metal bath,

and said retort having a continuous outflow for said body of hydrocarbon oil, means without the retort but for separating from the hydrocarbon oil the carbon resulting from the decomposition, and means for operatively connectingsaid separating means with the conduits whereby the 15. The process of converting associated therewith body of oil from which the carbon has been removed is returned for submergence -beneath the metal bath in the retort.

12. An, apparatus for converting hydrocarbon oils into more volatile products, com-i prising a retort having depending from the bottom thereof a plurality of chambers, a bath of non-evaporable metal filling said chambers and overlyin the bottom of the container, .a hydrocarbon oil inlet conduit leading to each chamber and having a discharge outlet for thejoil arranged at a point adjacent the lower end of said chambers and opening directly into said bath of metal, a protecting covering for said conduits-to prevent premature decomposition of the contained hydrocarbon oils, means for imparting to the metal constituting the bath heat suflicient to decompose the'hydrocarbons, and means for removing the formed carbon sediment accumulating upon the surface of the bath. i

13. In the cracking of hydrocarbon oils, the described process consisting inpassingthe oil in a substantially unvaporized and undissociated state upwardly through i a molten metal bath in a retort, collecting the resulting vapors and gases in the upper part 1 of the retort, conveying them away and condensing them, and continuously supplying directly to and continuously withdrawing from the surface ofthe bath a layer of the heavy fractions and unvaporized hydrocarbons which holds the carbon impurities in suspension, .and continuously separating the carbon therefrom.

14. The process of cracking hydrocarbon oils, consisting in passing the hydrocarbon oil before substantial evaporation or dissociation through a molten metal bath'in a retort, continuously supplying directly to the upper surface of such bath and continuously withdrawing from said'surface, a layer of unvaporized hydrocarbons which holds the carbon impurities in suspension, and separating-the carbon impurities. I

hydrocarbon oils into more volatile products, which consists in submerging the hydrocarbon oil, ,before evaporization or dissociation, beneath a molten metal fluid maintained at a suflicient temperature to decompose said hydrocarbon oil as it passes upwardly through said fluid, withdrawing the resultant vapor from a point above the molten fluid, maintaining on the surface of the bath a layer of hydrocar bon oil, by introducing said oil from the outside directly to the surface of said bath, whereby the carbon produced in the treatment is mixed therewith, and continuously removing the unvaporized hydrocarbon which holds the carbon impurities in suspension. 1 1 l 16. An apparatus for converting hydrocarbon oils into more volatile products, com

. the hydrocarbon oil without evaporization and dissociation at the lower portion of said bath of metal, means for imparting to the metal constituting the bath heat sufiicient to decompose the hydrocarbons, means leading through the wall of the retort to directly supply to the upper surface of said batha layer of hydrocarbon oil, and means causing the continuous discharge of the formed carbon sediment accumulating upon the surface of the bath.

17. In an apparatus for converting hydrocarbon oils into more volatile products, the

combination of a retort having therein a molten metal bath, conduits constructed and arran ed to deliver the hydrocarbon oil to be treate at a point adjacent the bottom of said bath, without said hydrocarbon oil becoming vaporized or dissociated, said retort having adjacent the top of said bath an inlet, and a. constantly open outlet, means for continuously introducing, through said inlet hydrocarbon oil to form a layer on said bath which finds a continuous exit through said outlet, and means for removing the vaporsformed.

18. In an apparatus for converting hydrocarbon oils into more volatile products, the combination of a retort having therein a molten metal bath, conduits constructed and arranged to deliver the hydrocarbon 'oil to be treated at a point adjacent the bottom of said bath without said hydrocarbon oil becoming vaporized or dissociated,-means for maintaining on the surface of the said bath a moving body of hydrocarbon oil, the said retort having an inlet in one wall above said surface for said oil to constitute the layer, and an outlet for the removal of hydrocarbon oil from the-surface of the bath, and means for separating the hydrocarbon from the latter.

In witness whereof we have hereunto signed our names.

WILLET C. WELLS. FRANK E. WELLS.

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